CN108690575A - A kind of modified epoxy pitch particle, full oil base drilling fluid and preparation method thereof - Google Patents
A kind of modified epoxy pitch particle, full oil base drilling fluid and preparation method thereof Download PDFInfo
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- CN108690575A CN108690575A CN201710227186.8A CN201710227186A CN108690575A CN 108690575 A CN108690575 A CN 108690575A CN 201710227186 A CN201710227186 A CN 201710227186A CN 108690575 A CN108690575 A CN 108690575A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/502—Oil-based compositions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
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Abstract
The invention discloses a kind of modified epoxy pitch particles, full oil base drilling fluid and preparation method thereof.The shell that the modified epoxy pitch particle includes the core being made of bituminous epoxy and is formed by modifying agent;The bituminous epoxy is obtained by the reaction with epoxy resin and curing agent again after grafting and activating by material asphalt and organic acid anhydride.The full oil base drilling fluid, is counted in parts by weight, including 90~95 parts of base oil, 1~3 part of organoclay, 1~5 part of emulsifier, 1~6 part of modified epoxy pitch particle.The modified epoxy pitch particle is that the sulphur of the bituminous epoxy and melting that will melt sprays into counter current contacting from reaction tower upper and lower ends respectively, and product is injected to chilling in quenching liquid and obtains;The drilling fluid is to be mixed to get each component.The present invention, as properties modifier, good graininess and high temperature deformation ability can be kept in full oil base drilling fluid, improves closure and filtrate reducing effect using modified epoxy pitch particle.
Description
Technical field
The invention belongs to oil drilling production technique fields, and in particular to a kind of modified epoxy pitch particle and preparation side
Method, and the full oil base drilling fluid using above-mentioned modified epoxy pitch particle as properties modifier.
Background technology
As oil-gas exploration is gradually to Deep Development, the chance for boring chance high temperature and pressure stratum gradually increases.These are all to boring
More stringent requirements are proposed for well liquid system.Compared with water-base drilling fluid, oil base drilling fluid has contamination resistance strong, lubricity
Good, strong inhibition capability is conducive to keep wellbore stability, can protect oil-gas Layer to the maximum extent, it is easy to maintain the features such as.Oil base drilling well
The excellent high-temperature stability of liquid and inhibition make it bore Holes of Complicated Wells, especially bore in high temperature deep well and water-sensitive strata, advantage
It is more obvious, and it can be effectively protected water sensitivity oil-gas Layer, improve oil and gas production.
Although there are many oil base drilling fluid advantage, in application, the high temperature resistance inorganic agent adapted to therewith in high temperature deep well
But at one of the factor for restricting its development.Fluid loss additive in inorganic agent be mainly used for control drilling fluid system filter loss and
Stability.For the use environment of this high temperature and pressure, foreign countries have developed one kind in oil base drilling fluid dissolubility it is good, anti-height
The strong oil-soluble polymerization composition granule fluid loss additive of warm ability.This polymer beads drop filter during can be externally formed with it is thin and
Yielding mud cake can block formation pore in internal polymer beads.Although such polymer can play preferable filtrate reducing
Effect, but it is expensive.
For asphalt product compared with special copolymer, cheap and material source is extensive, is domestic and international modern drilling work
One of indispensable important dose of kind of journey has good anti-collapse, lubrication, reduces the comprehensive effectivenesses such as leak-off and high-temperature stable.So
And general softening point asphalt can cannot be satisfied the high-temperature operation requirement under deep-well because even trickling is overbated.
High softening point bitumen refers to softening point at 100 DEG C or more, especially in 120 DEG C or more of pitch.High softening-point drips
Blueness has to compare due to its outstanding high-temperature resistance to be widely applied.High softening point bitumen can be used for the brill in deep-seated oil gas field
In well operations, as the important component of drilling fluid, closure, anti-collapse, stabilizing borehole can be played under the high temperature conditions, reduced
The effect of filter loss.
General high softening point bitumen is mostly asphalt, coal tar pitch, bitumen etc..Bituminous epoxy refers to adding in pitch
It after entering epoxy resin, by physical blending, crosslinks and reacts with curing agent again after stable and uniform, form a kind of high property of multicomponent
The solidfied material of energy.Wherein, different bituminous epoxies is formed, performance is also different.In entire bituminous epoxy, if epoxy systems
It accounts for leading, then forms irreversible thermosets;If asphalt system accounts for leading, it is formed with the high softening of part thermoplastic
Point pitch.
But high softening point bitumen is when being ground into particle applied in drilling fluid system, due to particle deformability phase
To limited, viscoplasticity is relatively poor, when irregular there are oil-gas Layer duct, the problems such as cannot being well embedded in wherein.And it is soft
Change point is higher, and the brittle property of pitch is more apparent, it is difficult to play good closure and filtrate reducing effect.CN102304353A and
CN103013460A discloses a kind of method for being mixed in a certain ratio rubber powder, bitumen and calcium carbonate superfine powder, crushing
Pitch particle composition is prepared, some is also added into polymer fiber etc..This method is only by rubber powder(With or polymer
Fiber)It is simply mixed with pitch, the two does not form organic whole, it is difficult to persistently be played in wider viscoelastic section
Effect.
In addition, pitch used is bitumen, softening point is not easy to control or between 80 to 120 DEG C, and the molten object content of oil is high
It up to 98% or more, is dissolved in oil phase in use, being substantially all in oil base drilling fluid, exists almost without pitch particle, it cannot
Stratum microcrack is effectively blocked, and high temperature resistant property is deteriorated.And the continuous phase that rubber powder is formed in white oil or diesel oil
Middle long-time impregnates swelling, it may occur that coalescence destroys the stability of entire drilling fluid system.
Invention content
For prior art preparation high softening point bitumen complex process and cost it is higher, and pitch particle is applied to full oil
It is high to there is oily solubility during base drilling fluid, pitch particle is lacked in drilling fluid system, stratum duct and crack is effectively sealed
The problems such as blocking up, making the increase of its filter loss, suspending power and high-temperature resistance variation, the present invention provides a kind of modified epoxy pitches
Particle, full oil base drilling fluid and preparation method thereof.And the full oil base drilling fluid of the present invention uses modified epoxy pitch particle as property
Energy conditioning agent, existing certain high-temperature resistance have certain high temperature deformability again, can play closure well, prevent
It collapses and filtrate reducing effect, while improving the large rock-carrying ability of drilling fluid.
First aspect present invention provides a kind of modified epoxy pitch particle, includes the core being made of bituminous epoxy and by changing
Property dosage form at shell, count in parts by weight, core be 7 ~ 9 parts, shell be 1 ~ 3 part;The modifying agent includes polymerised sulphur and free sulphur, is changed
Property agent in polymerised sulphur and the weight ratio of free sulphur be 3:7~7:3, preferably 4:6~7:3;The bituminous epoxy is by material asphalt
It is obtained by the reaction with epoxy resin and curing agent again after grafting and activating with organic acid anhydride.
The organic acid anhydride is unitary and/or multicomponent organic acid acid anhydride, preferably maleic anhydride, poly- ethanedioic acid acid anhydride, poly- penta
At least one of dicarboxylic anhydride, poly- azelaic acid acid anhydride and polyisobutylene butanedioic anhydride, the addition of organic acid anhydride accounts for material asphalt weight
Amount 2% ~ 20%.
The material asphalt is at least one of decompression residuum, oxidized asphalt, solvent deasphalting, bitumen, softening
Point is 30 ~ 70 DEG C.
The epoxy resin be bisphenol A type epoxy resin, epoxide equivalent be 180 ~ 280 grams/equivalent, preferably CYD-127,
At least one of CYD-128, CYD-134, E-42, E-44 etc., further preferably at least one of CYD-128, E-44,
The addition of epoxy resin is the 5% ~ 30% of material asphalt weight.
The curing agent is aliphatic amine, preferably long-chain fat race amine, further preferably hydrogenated-tallow group primary
Amine, hydrogenated-tallow group trimethylene diamines, cocoyl 1,3- trimethylene diamines, hexadecyldimethyl benzyl ammonium tertiary amine, octadecyldimethyl uncle
One or more of amine, the addition of curing agent are account for material asphalt weight 5% ~ 20%.
The average grain diameter of the modified epoxy pitch particle preferably≤150 μm.
Second aspect of the present invention provides a kind of full oil base drilling fluid, counts in parts by weight, including following component:
90~95 parts of base oil,
1~3 part of organoclay,
1~5 part of emulsifier,
1~6 part of the modified epoxy pitch particle,
In the full oil base drilling fluid, the base oil is diesel oil, biodiesel, white oil, at least one of vegetable oil, preferably
White oil.
In the full oil base drilling fluid, the emulsifier is aliphatic acid polyethenoxy ether series, alkylphenol-polyethenoxy
Ether series or polyoxyethylene carboxylate series, aliphatic acid polyethenoxy ether series preferably oleic acid polyoxyethylene, stearic acid are poly-
At least one of ethylene oxide ether and lauric acid polyoxyethylene ether, the preferred Nonyl pheno of alkyl phenol polyoxyethylene ether series
At least one of ether, octyl phenol polyoxyethylene ether and alkyl phenol polyoxyethylene ether, the preferred pine of polyoxyethylene carboxylate series
At least one of fragrant acid polyoxyethylene ester, polyoxyethylene oleic acid ester and polyoxyethylene stearic acid ester.
Further include heavy weight additive in the full oil base drilling fluid, regulating density of drilling liquid reaches 1.50~2.10g/cm3,
The heavy weight additive is barite and/or lime stone.
Third aspect present invention provides the preparation method of the modified epoxy pitch particle, includes the following steps:
(1), Cosan is heated to 250 ~ 350 DEG C, 10 ~ after sixty minutes, stabilizer is added, while being passed through inert gas, keeps
0.5 ~ 2.0MPa of pressure reacts 10 ~ 100 minutes, sulfur melting is made to polymerize, and forms liquid modifier;
(2), material asphalt is heated to molten condition, organic acid anhydride is added, and being passed through inert gas makes reactor pressure keep
In 0.2 ~ 2.0MPa, reaction temperature is 150 ~ 250 DEG C, reacts 2 ~ 8 hours, obtains grafting and activating pitch;By grafting and activating pitch
100 ~ 150 DEG C are cooled to, curing agent is added and stirs evenly, epoxy resin is then added, continues stirring 10 ~ 30 minutes, is changed
Property bituminous epoxy;
(3), by step(1)Liquid modifier and step(2)Modified epoxy pitch respectively from reaction tower both ends spray into, by sulphur
Sulphur:The weight ratio of modified epoxy pitch is 1 ~ 3:7 ~ 9, make the two counter current contacting, is kept for 10 ~ 60 minutes;
(4), by step(3)Obtained product, which is injected in 10 ~ 50 DEG C of quenching liquid, carries out chilling, forms the ring of coating modification agent
Oxygen pitch particle, and be suspended in quenching liquid, it is kept for 30 ~ 120 minutes, is then dehydrated, is dried and is sieved, obtain modified ring
Oxygen pitch particle.
In modified epoxy pitch particle of the present invention, step(1)Described in stabilizer be can be with polymerised sulphur strand two
Hold the substance of sulphur atom bonding, preferably one in monoolefine, alkadienes, halogenated dienes hydrocarbon, halogenated aryl hydrocarbon, nitro halogenated aryl hydrocarbon
Kind is a variety of, further preferably 1- dodecylenes, tetradecene, 1- octadecenes, butadiene, chlorobutadiene, isoamyl two
At least one of alkene, hexachloroparaxylene (HPX), iodonitrobenzene and bromo nitryl benzene.Step(2)Described in organic acid anhydride be one
Member and/or multicomponent organic acid acid anhydride, preferably maleic anhydride, poly- ethanedioic acid acid anhydride, poly- glutaric anhydride, poly- azelaic acid acid anhydride and poly- isobutyl
At least one of alkene succinic anhydride.
Preferably, the addition of the stabilizer is the 0.01% ~ 0.5% of sulphur weight.
In the preparation method, weight concentration of the stabilizer in quenching liquid is 0.001% ~ 0.1%, quenching liquid
Temperature is 10 ~ 50 DEG C, and the time that progress chilling is contacted with quenching liquid is 30 ~ 120 minutes.
In the preparation method, the Cosan of 99.5% or more the sulphur preferred weight purity, the quenching liquid is preferred
For water.
Fourth aspect present invention provides the preparation method of the full oil base drilling fluid, includes by certain proportioning by each group
Divide mixing, selectively adds heavy weight additive, obtain full oil base drilling fluid.
In the preparation method of the full oil base drilling fluid of the present invention, it is by the sequence that each component mixes by certain proportioning:First exist
Emulsifier is added in base oil, stirs, adds organoclay, stirs, adds modified epoxy pitch particle, stirs.If you need to adjust
Drilling fluid density adds heavy weight additive.
In the preparation method of the full oil base drilling fluid of the present invention, the purpose of above-mentioned triple mixing is uniformly mixed, can be adopted
Time is followed successively by 15~20 minutes, 5~10 minutes, 20~40 minutes.
It is complete in drilling fluid, can be used not only for can be used as properties modifier for the modified epoxy pitch particle of the present invention
Oil base drilling fluid can be also used for Water-In-Oil or water-base drilling fluid, in the case of being high temperature especially suitable for use environment.
Compared with prior art, the present invention haing the following advantages:
(1)The residual oil of common softening point or pitch can be prepared into the high ring of softening point by the present invention by suitable epoxy technique
Oxygen pitch.And using bituminous epoxy as nuclear phase, using the modifying agent including polymerised sulphur and free sulphur as shell, makes bituminous epoxy and change
Property agent be organically combined as a whole, and polymerised sulphur have certain viscoplasticity, not only increase the high temperature resistant property of particle, simultaneously
Also increase its deformability.
(2)In the preparation method of the modified epoxy pitch particle of the present invention, graft reaction first is carried out to material asphalt, is made
Part asphaltene molecule has been grafted organic acid anhydride molecule, and asphalt surface is provided with active group, then again with epoxy resin and solidification
Agent carries out curing reaction, curing reaction can be made to be easier to make for, and gained bituminous epoxy property is more stablized, without being added
Accelerating agent.
(3)During bituminous epoxy is modified agent cladding, bituminous epoxy surface active groups can be with polymerised sulphur two
The free radical at end combines, and plays stabilization, improves the yield of high-elastic polymerised sulphur, therefore, only need to be in sulfur melting polymerization stage
When stabilizer is added, without adding other stabilizers in quenching process, you can reach stablizing effect, simplify technique mistake
Journey.Bituminous epoxy is introduced in the sulphur melt polymerization later stage, high-elastic polymerised sulphur can be made to form one layer of clad outside bituminous epoxy,
After subsequently cooling, stable processing, organic whole is formed, the performance of pitch particle is improved.
(4)In the preparation method of the modified epoxy pitch particle of the present invention, inertia is introduced in sulphur polymerization process
Gas(Such as N2), on the other hand it is to provide foot to the sulphur atomization after polymerization first, in order to play a protective role at high temperature
Enough power;Further, it is also possible to by the adjustment of pressure, carry out the particle size of the final particle of modulation, to meet different make
With requiring.
(5)In general, after sulphur frit reaction, the conversion ratio of high-elastic polymerised sulphur can reach 40% ~ 70%.The method of the present invention
In do not need to the processing such as extract it, purify, although because the sulphur that this part does not convert cannot be with bituminous epoxy shape
At organic whole, but it is good dispersant and interleaving agent, the particle obtained in the process of the present invention without it is additional its
Its auxiliary agent, simplifies production technology.
(6)The crack or duct of oil-gas Layer are not of uniform size, and the deformability of simple pitch particle is limited after all, cannot
Good match therewith, therefore the problems such as easily cause the duct that cannot be arbitrarily embedded into all size and shapes in well, it is difficult to it rises
It is blocked and filtrate reducing effect to ideal;The present invention is used using bituminous epoxy as nuclear phase, using the modifying agent containing polymerised sulphur as shell
The modified epoxy pitch particle that layer obtains, that is, increase its viscoelastic use scope, can make in wider pore size distribution range
With, play the role of it is good closure and stabilizing borehole.
(7)The full oil base drilling fluid of the present invention uses modified epoxy pitch particle, existing certain high-temperature resistance to have again
Certain high temperature deformability can play closure, anti-collapse and filtrate reducing effect well, while improve taking for drilling fluid
Rock ability.
Specific implementation mode
Following non-limiting embodiments can make those skilled in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Embodiment 1
The residual oil that 360g softening points are 41.6 DEG C is heated to 155 DEG C in pitch reaction kettle, 10.8g maleic acids are added
Acid anhydride, and it is passed through N2So that pitch reactor pressure is maintained at 0.9MPa, reacts 4.5 hours, obtain grafting and activating pitch.Grafting is lived
Change pitch and be cooled to 125 DEG C, 50.4g cocoyls 1 are added, 3- trimethylene diamines stirs evenly, and 72g CYD-128 type rings are then added
Oxygen resin continues stirring 18 minutes, obtains modified epoxy pitch;120g Cosans are placed in closed reaction of Salmon-Saxl kettle, are heated to
The isoprene of 0.10g is added after 290 DEG C, 50 minutes, while being passed through N2Keep pressure 1.2MPa.Wait for that pitch graft reaction is completed
Afterwards, the valve for opening simultaneously reaction kettle sprays into two kinds of liquid in contact towers, and molten sulfur enters from tower top, molten asphalt from
Tower lower part enters, and the two is made to carry out sufficient counter current contacting, is kept for 35 minutes.Contact tower bottom discharge valve is opened, liquid is fast
Speed, which is injected in cold water, carries out chilling, forms uniform pitch and is coated with the particle of modifying agent, and is suspended in quenching liquid.
It is kept for 50 minutes under the conditions of 30 DEG C, adequately cure and stablize, then carry out dehydration and vacuum drying processing.By institute
It obtains solid to be sieved with vibrating screen, obtains modified epoxy pitch particle.
90 parts by weight 5# white oils are taken, 4.5 parts by weight oleic acid polyoxyethylenes are added, at normal temperatures high-speed stirred 15 minutes,
2.5 parts by weight organoclays are added, stir 10 minutes, add the modified epoxy pitch combination for accounting for 3.0 parts by weight of drilling fluid total amount
Composition granule continues stirring 20 minutes, and barite is added and drilling fluid density is adjusted the full oil base drilling well for obtaining stabilization to desired value
Liquid.
Embodiment 2
The oxidized asphalt that 300g softening points are 52.2 DEG C is heated to 170 DEG C in pitch reaction kettle, the poly- ethanedioic acids of 13.8g are added
Acid anhydride, and it is passed through N2So that pitch reactor pressure is maintained at 1.6MPa, reacts 5.0 hours, obtain grafting and activating pitch.Grafting is lived
Change pitch and be cooled to 130 DEG C, 28.6g octadecyldimethyl tertiary amines are added, stir evenly, 36.5g CYD-128 are then added
Type epoxy resin continues stirring 20 minutes, obtains bituminous epoxy;150g Cosans are placed in closed reaction of Salmon-Saxl kettle, are heated to
The 1- 12 of 0.24g is added after 300 DEG C, 50 minutes(Carbon)Alkene, while being passed through N2Keep pressure 1.5MPa.Wait for pitch graft reaction
After the completion, the valve for opening simultaneously reaction kettle sprays into two kinds of liquid in contact tower, and molten sulfur enters from tower top, melting drip
Blueness enters from tower lower part, and the two is made to carry out sufficient counter current contacting, is kept for 40 minutes.Contact tower bottom discharge valve is opened, by liquid
Body, which is quickly injected in cold water, carries out chilling, forms uniform pitch and is coated with the particle of modifying agent, and is suspended in quenching liquid
In the middle.It is kept for 55 minutes under the conditions of 45 DEG C, adequately cure and stablize, then carry out at dehydration and vacuum drying
Reason.Obtained solid is sieved with vibrating screen, obtains modified epoxy pitch particle.
91 parts by weight 3# white oils are taken, 3 parts by weight lauric acid polyoxyethylene ether are added, at normal temperatures high-speed stirred 20 minutes,
1.5 parts by weight organoclays are added, stirs 5 minutes, adds the modified epoxy bituminous composition for accounting for 4.5 parts by weight of drilling fluid total amount
Particle continues stirring 25 minutes, and barite is added and drilling fluid density is adjusted the full oil base drilling well for obtaining stabilization to desired value
Liquid.
Embodiment 3
The solution-off pitch that 450g softening points are 61.2 DEG C is heated to 175 DEG C in pitch reaction kettle, 28.4g polyisobutene is added
Succinic anhydride, and being passed through inert gas makes pitch reactor pressure be maintained at 1.3MPa, reacts 6.0 hours, obtains grafting and activating
Pitch.Grafting and activating pitch is cooled to 140 DEG C, 85.6g hydrogenated-tallow group trimethylene diamines is added, stirs evenly, is then added
105g E-44 type epoxy resin continues stirring 25 minutes, obtains bituminous epoxy;200g Cosans are placed in closed reaction of Salmon-Saxl kettle
In, it is heated to that the hexachloroparaxylene (HPX) of 0.32g is added after 310 DEG C, 55 minutes, while being passed through N2Keep pressure 1.2MPa.It waits dripping
After the completion of green graft reaction, open simultaneously the valve of reaction kettle, two kinds of liquid sprayed into contact towers, molten sulfur from tower top into
Enter, molten asphalt enters from tower lower part, and the two is made to carry out sufficient counter current contacting, is kept for 45 minutes.Contact tower bottom is opened to put
Expect valve, liquid is quickly injected in cold water and carries out chilling, uniform pitch is formed and is coated with the particle of modifying agent, and suspend
In quenching liquid.It is kept for 45 minutes under the conditions of 45 DEG C, adequately cure and stablize, be then dehydrated and vacuumized
It is dried.Obtained solid is sieved with vibrating screen, obtains modified epoxy pitch particle.
92 parts of 5# white oils are taken, 3.0 parts of nonylphenol polyoxyethylene ether are added, at normal temperatures high-speed stirred 20 minutes, are added 1 part
Organoclay stirs 10 minutes, adds the modified epoxy Asphalt composition particle for accounting for 4.0 parts by weight of drilling fluid total amount, continue to stir
It mixes 30 minutes, barite is added and drilling fluid density is adjusted the full oil base drilling fluid for obtaining stabilization to desired value.
Embodiment 4
The oxidized asphalt that 200g softening points are 69.4 DEG C is heated to 180 DEG C in pitch reaction kettle, the poly- glutaric acids of 16.2g are added
Acid anhydride, and it is passed through N2So that pitch reactor pressure is maintained at 1.5MPa, reacts 8 hours, obtain grafting and activating pitch;By grafting and activating
Pitch is cooled to 145 DEG C, and 35.2g octadecyldimethyl tertiary amines are added, stir evenly, and 54.2g CYD-128 types are then added
Epoxy resin continues stirring 25 minutes, obtains bituminous epoxy;50g Cosans are placed in closed reaction of Salmon-Saxl kettle, are heated to 340
DEG C, the 1- 18 of 0.1g is added after forty minutes(Carbon)Alkene, while being passed through N2Keep pressure 1.8MPa.Wait for that pitch graft reaction is completed
Afterwards, the valve for opening simultaneously reaction kettle sprays into two kinds of liquid in contact towers, and molten sulfur enters from tower top, molten asphalt from
Tower lower part enters, and the two is made to carry out sufficient counter current contacting, is kept for 50 minutes.Contact tower bottom discharge valve is opened, liquid is fast
Speed, which is injected in cold water, carries out chilling, forms uniform pitch and is coated with the particle of modifying agent, and is suspended in quenching liquid.
It is kept for 35 minutes under the conditions of 35 DEG C, adequately cure and stablize, then carry out dehydration and vacuum drying processing.By institute
It obtains solid to be sieved with vibrating screen, obtains modified epoxy pitch particle.
93 parts of 5# white oils are taken, 1.5 parts of stearic acid polyoxyethylene ethers are added, at normal temperatures high-speed stirred 15 minutes, are added 2.0
Part organoclay, stirs 10 minutes, adds the modified epoxy Asphalt composition particle for accounting for 3.5 parts by weight of drilling fluid total amount, continues
Stirring 25 minutes is added barite and drilling fluid density is adjusted the full oil base drilling fluid for obtaining stabilization to desired value.
Comparative example
The oxidized asphalt 65g that softening point is 142.5 DEG C and the coal tar pitch 35g that softening point is 145.6 DEG C are taken, butadiene-styrene rubber glue is taken
Powder 75g, is placed in household freezer and freezes(- 35 DEG C of cryogenic temperature, cooling time are 12 hours).6.5g hydrotalcites and 7.8g ten is added
Six alkyl trimethyl ammonium chlorides.Crush 25s in Miniature universal pulverizer, sieved to get high softening point bitumen with vibrating screen and
Rubber particle composite.
90 parts by weight 5# white oils are taken, 5 parts by weight oleic acid polyoxyethylenes are added, high-speed stirred 15 minutes, add at normal temperatures
Enter 2 parts by weight organoclays, stir 5 minutes, add the high softening point bitumen composition grain for accounting for 3 parts by weight of drilling fluid total amount,
Continue stirring 20 minutes, barite is added and drilling fluid density is adjusted the full oil base drilling fluid for obtaining stabilization to desired value.
To passing through after polymerised sulphur/free sulphur of gained modified pitch particle, grain size, softening point and sieve in the various embodiments described above
Rate is tested.Wherein, the sulphur for being dissolved in carbon disulfide is free sulphur, and the sulphur insoluble in carbon disulfide is polymerised sulphur, result
As shown in table 1.
The property of modified pitch particle in 1. each embodiment of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Polymerised sulphur/free sulphur | 6.4:3.6 | 5.9:4.1 | 6.8:3.2 | 6.5:3.5 |
| Softening point, DEG C | 128.4 | 142.9 | 153.6 | 162.4 |
| Average particle size, μm | 125 | 109 | 96 | 106 |
| Percent of pass after sieve, % | 97.0 | 96.4 | 98.2 | 98.6 |
Average particle size refers to using certain pore size(Or mesh number)Standard screen particle is sieved, if percent of pass 90% with
On, then the aperture of standard screen used is the average particle size of particle.Percent of pass refers to after sieve:After particulate matter room temperature is stacked 30 days, use
It is sieved with the standard screen of same apertures when rigid prepare, the percentage of gross mass is accounted for by the granular mass of sieve pore.The index
The main stability for investigating particulate matter after storage, i.e. change of size situation.
The property for measuring drilling fluid in above-described embodiment and comparative example respectively, is shown in Table 2.
The performance of 2 full oil base drilling fluid of table
| ρ/g.cm-3 | AV/mPa.s | PV/mPa.s | YP/Pa | YP/PV | FLHTHP/ml | ES/V | |
| Embodiment 1 | 1.6 | 31.8 | 27.9 | 12.0 | 0.43 | 5.0 | 2200 |
| Embodiment 2 | 1.5 | 32.0 | 24.8 | 12.2 | 0.49 | 4.8 | 2180 |
| Embodiment 3 | 1.8 | 32.4 | 25.6 | 11.7 | 0.46 | 4.2 | 2100 |
| Embodiment 4 | 1.7 | 33.5 | 25.4 | 12.8 | 0.50 | 3.5 | 2210 |
| Comparative example | 1.6 | 36.6 | 31.0 | 9.0 | 0.29 | 35.6 | 1850 |
Note:Hot rolling condition:Time is 16 hours, 180 DEG C of temperature;
Rheological characteristic test temperature is 60 DEG C,
High temperature and high pressure filter loss determination condition:180 DEG C, 3.5MPa,
Wherein:AV:Apparent viscosity,
PV:Plastic viscosity,
YP:Yield value,
YP/PV:Ratio of dynamic shear force/yield value to plastic viscosity,
FLHTHP:High temperature and high pressure filter loss,
ES:Emulsion-breaking voltage.
The full oil base drilling fluid containing modified epoxy pitch particle of the present invention has lower plastic viscosity, higher
Yield value, ratio of dynamic shear force/yield value to plastic viscosity and emulsion-breaking voltage improve the high-temperature resistance and large rock-carrying ability of system.
Claims (19)
- The shell that 1. a kind of modified epoxy pitch particle includes the core being made of bituminous epoxy and is formed by modifying agent, by weight Number meter, core are 7 ~ 9 parts, and shell is 1 ~ 3 part;The modifying agent includes polymerised sulphur and free sulphur, polymerised sulphur and free sulphur in modifying agent Weight ratio be 3:7~7:3, preferably 4:6~7:3;The bituminous epoxy is by material asphalt and organic acid anhydride through grafting and activating It is obtained by the reaction with epoxy resin and curing agent again afterwards.
- 2. modified epoxy pitch particle described in accordance with the claim 1, it is characterised in that:The organic acid anhydride be unitary and/or Multicomponent organic acid acid anhydride, preferably maleic anhydride, poly- ethanedioic acid acid anhydride, poly- glutaric anhydride, poly- azelaic acid acid anhydride and polyisobutene fourth two The addition of at least one of acid anhydrides, organic acid anhydride accounts for material asphalt weight 2% ~ 20%.
- 3. modified epoxy pitch particle described in accordance with the claim 1, it is characterised in that:The material asphalt be decompression residuum, At least one of oxidized asphalt, solvent deasphalting, bitumen, softening point are 30 ~ 70 DEG C.
- 4. according to any modified epoxy pitch particles of claim 1-3, it is characterised in that:The epoxy resin is bis-phenol A type epoxy resin, epoxide equivalent are 180 ~ 280 grams/equivalent, preferably CYD-127, CYD-128, CYD-134, E-42, E-44 At least one of Deng, further preferably at least one of CYD-128, E-44, the addition of epoxy resin drip for raw material The 5% ~ 30% of green weight.
- 5. according to any modified epoxy pitch particles of claim 1-3, it is characterised in that:The curing agent is aliphatic Amine, preferably long-chain fat race amine, further preferably hydrogenated-tallow group primary amine, hydrogenated-tallow group trimethylene diamines, cocounut oil Base 1, one or more of 3- trimethylene diamines, hexadecyldimethyl benzyl ammonium tertiary amine, octadecyldimethyl tertiary amine, curing agent add It is account for material asphalt weight 5% ~ 20% to enter amount.
- 6. modified epoxy pitch particle described in accordance with the claim 1, it is characterised in that:The modified epoxy pitch particle is put down Equal grain size≤150 μm.
- 7. a kind of full oil base drilling fluid, is counted in parts by weight, including following component:90~95 parts of base oil1~3 part of organoclay1~5 part of emulsifier1~6 part of properties modifier,The properties modifier is using any modified epoxy pitch particle of claim 1 ~ 6.
- 8. full oil base drilling fluid according to claim 7, it is characterised in that:The emulsifier is aliphatic acid polyethenoxy ether Series, alkyl phenol polyoxyethylene ether series or polyoxyethylene carboxylate series;The preferred oleic acid of aliphatic acid polyethenoxy ether series At least one of polyoxyethylene ether, stearic acid polyoxyethylene ether and lauric acid polyoxyethylene ether, alkyl phenol polyoxyethylene ether system Arrange at least one of preferred nonylphenol polyoxyethylene ether, octyl phenol polyoxyethylene ether and alkyl phenol polyoxyethylene ether, aliphatic acid At least one in polyoxyethylene ester series preferably polyoxylethylene abietate, polyoxyethylene oleic acid ester and polyoxyethylene stearic acid ester Kind.
- 9. full oil base drilling fluid according to claim 7, it is characterised in that:The base oil is diesel oil, biodiesel, white At least one of oil, vegetable oil, preferably white oil.
- 10. full oil base drilling fluid according to claim 7, it is characterised in that:In the full oil base drilling fluid, further include Heavy weight additive, regulating density of drilling liquid reach 1.50~2.10g/cm3, the heavy weight additive is barite and/or lime stone.
- 11. the preparation method of any modified epoxy pitch particle of claim 1 ~ 6, includes the following steps:(1), Cosan is heated to 250 ~ 350 DEG C, 10 ~ after sixty minutes, stabilizer is added, while being passed through inert gas, keeps 0.5 ~ 2.0MPa of pressure reacts 10 ~ 100 minutes, sulfur melting is made to polymerize, and forms liquid modifier;(2), material asphalt is heated to molten condition, organic acid anhydride is added, and being passed through inert gas makes reactor pressure keep In 0.2 ~ 2.0MPa, reaction temperature is 150 ~ 250 DEG C, reacts 2 ~ 8 hours, obtains grafting and activating pitch;By grafting and activating pitch 100 ~ 150 DEG C are cooled to, curing agent is added and stirs evenly, epoxy resin is then added, continues stirring 10 ~ 30 minutes, is changed Property bituminous epoxy;(3), by step(1)Liquid modifier and step(2)Modified epoxy pitch respectively from reaction tower both ends spray into, by sulphur Sulphur:The weight ratio of modified epoxy pitch is 1 ~ 3:7 ~ 9, make the two counter current contacting, is kept for 10 ~ 60 minutes;(4), by step(3)Obtained product, which is injected in quenching liquid, carries out chilling, forms the bituminous epoxy of coating modification agent Grain, and be suspended in quenching liquid, it is kept for 30 ~ 120 minutes, is then dehydrated, is dried and is sieved, obtain modified epoxy pitch Grain.
- 12. the preparation method of modified epoxy pitch particle according to claim 11, it is characterised in that:The stabilizer is It can be with the substance of polymerised sulphur strand both ends sulphur atom bonding, preferably monoolefine, alkadienes, halogenated dienes hydrocarbon, halogenated virtue It is one or more in hydrocarbon, nitro halogenated aryl hydrocarbon, further preferably 1- dodecylenes, tetradecene, 1- octadecenes, fourth At least one of diene, chlorobutadiene, isoprene, hexachloroparaxylene (HPX), iodonitrobenzene and bromo nitryl benzene;It is described steady The addition for determining agent is the 0.01% ~ 0.5% of sulphur weight.
- 13. the preparation method of modified epoxy pitch particle according to claim 11, it is characterised in that:Step(4)In, institute It is 0.001% ~ 0.1% to state weight concentration of the stabilizer in quenching liquid, and the temperature of quenching liquid is 10 ~ 50 DEG C, is contacted with quenching liquid The time for carrying out chilling is 30 ~ 120 minutes.
- 14. the preparation method of modified epoxy pitch particle according to claim 11, it is characterised in that:The sulphur selection The Cosan of 99.5% or more purity by weight, the quenching liquid are water.
- 15. the preparation method of any full oil base drilling fluid of claim 7 ~ 10, including:Each component is mixed according to the ratio, Heavy weight additive is selectively added, full oil base drilling fluid is obtained.
- 16. the preparation method of full oil base drilling fluid according to claim 15, it is characterised in that:Each component is mixed suitable Sequence is as follows:Emulsifier is first added in base oil, stirs, adds organoclay, stirs, adds modified epoxy pitch particle, stirs, Obtain full oil base drilling fluid.
- 17. the preparation method of full oil base drilling fluid according to claim 16, it is characterised in that:The triple mixing Time is followed successively by 15~20 minutes, 5~10 minutes, 20~40 minutes.
- 18. the preparation method of full oil base drilling fluid according to claim 15, it is characterised in that:The modified epoxy drip Green particle is prepared by either method described in claim 11 ~ 14.
- 19. application of any modified epoxy pitch particle of claim 1 ~ 6 in drilling fluid.
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| CN112210221A (en) * | 2019-07-10 | 2021-01-12 | 中国石油化工股份有限公司 | Epoxy asphalt material and preparation method thereof |
| CN115232604A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Drilling fluid plugging agent and preparation method thereof |
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